Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
  • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
  • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
  • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
  • A01N43/647—Triazoles; Hydrogenated triazoles
  • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
  • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
  • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
  • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
  • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles

Definitions

• the present invention relates to vinyl azoles, processes for their preparation, fungicides which contain these compounds as active ingredients, and a process for combating fungi with these compounds.
• the compounds of formula I can exist as E / Z isomers. Under the name Vinylazole are demented . speaking to understand both the pure isomers and their mixtures.
• mixtures of compounds can be formed which are identical in terms of R, X, Z and n, but which differ in the position of the double bond. These mixtures are encompassed by Formula I; in the description they are characterized by the information a / b on the position of the double bond.
• R denotes hydrogen, an unbranched or branched alkyl radical having 1 to 7 carbon atoms, such as methyl, ethyl, isopropyl, n-propyl, tert-butyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, or a phenyl radical which can be mono- or polysubstituted by halogen, such as chlorine or bromine, such as 4-chlorophenyl, 2,4-dichlorophenyl, 4-bromophenyl.
• halogen such as chlorine or bromine
• X in formula I means, in addition to hydrogen or phenyl, halogen, such as chlorine, bromine, iodine, or an unbranched or branched alkyl radical having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, sec-butyl, isobutyl, tert-butyl.
• halogen such as chlorine, bromine, iodine
• an unbranched or branched alkyl radical having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, sec-butyl, isobutyl, tert-butyl.
• Preferred compounds of the formula I are those in which R is an alkyl radical and the double bond is in position a or b.
• X in these preferred compounds is, for example, 2-chloro, 4-bromo, 2,4-dichloro, 4-methyl, 4-phenyl.
• the vinyl azoles of the formula I are obtained by eliminating HY from compounds of the formulas in which R, X, Z and n have the meanings given above and Y represents a leaving group.
• the vinyl azoles of the formula I are obtained by eliminating water in the presence of an acidic dehydration catalyst from the corresponding ⁇ -azolyl alcohols of the formulas II and III.
• Suitable catalysts are protonic acids, Lewis acids, acid anhydrides or acid chlorides, for example sulfuric, phosphoric or formic acid, p-toluenesulfonic acid, boron trifluoride, diphosphorus pentoxide, acetic anhydride, phosphorus oxychloride, thionyl chloride.
• the amount of acid catalyst is 10 to 200% by weight of the ⁇ -azolyl alcohol.
• the elimination of water is carried out at a temperature in the range between 70 and 180 ° C., preferably between 80 and 120 ° C. It can be carried out in a solvent-free medium. However, it is preferred to work in the presence of a solvent.
• Suitable solvents for this are toluene, xylene, pyridine, glacial acetic acid, acetonitrile.
• the hydroxy function can also be converted into a more easily removable group, for example in tosylate, halide or acetate.
• This leaving group can then in the presence of a basic catalyst, for example an alcoholate, a tertiary amine, an alkali carbonate, such as v ⁇ Sodium methylate, sodium ethylate, potassium tert-butoxide, pyridine, or cleave, potassium carbonate, in the presence of sodium sulfide at a temperature between 20 and 100 o C.
• a basic catalyst for example an alcoholate, a tertiary amine, an alkali carbonate, such as v ⁇ Sodium methylate, sodium ethylate, potassium tert-butoxide, pyridine, or cleave, potassium carbonate
• the elimination reaction is preferably carried out in the presence of a solvent.
• Suitable solvents are aliphatic alcohols, such as ethanol, n-butanol, tert-butanol, octanol, chlorinated hydrocarbons, such as chloroform, dichloromethane, N, N-dialkylamides, such as dimethylformamide, and also dimethyl sulfoxide, pyridine, toluene, tetrahydrofuran, water. Mixtures of these solvents can also be used.
• the hydroxy function can also be esterified, i.e. be converted into an acetate or xanthate group, which can then be thermally eliminated by known methods (Houben-Weyl, Methods of Organic Chemistry, Vol. 5 / 1b, p. 109 ff, Georg Thieme-Verlag, Stuttgart, 1972).
• the vinyl azoles of the formula I can be converted in a conventional manner into salts or metal complexes which are compatible with plants.
• Mineral acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid and organic acids such as acetic acid and dodecylbenzenesulfonic acid are suitable for salt formation.
• the fungicidal activity of the salts of vinyl azoles is based on the cation, so that the anion can be selected from the large number of anions which are tolerated by plant physiology.
• Metal complexes can be formed by the addition of the vinyl azoles to the cations of metal salts. Copper, zinc, iron, manganese and nickel salts, such as copper (II) chloride, copper (II) sulfate, copper (II) nitrate, zinc (II) chloride, iron (III ) chloride, manganese (II) chloride, nickel (II) bromide.
• Copper, zinc, iron, manganese and nickel salts such as copper (II) chloride, copper (II) sulfate, copper (II) nitrate, zinc (II) chloride, iron (III ) chloride, manganese (II) chloride, nickel (II) bromide.
• the following vinyl azoles of the formula I can be prepared analogously.
• the new active ingredients show a strong fungitoxic activity against phytopathogenic fungi, especially from the classes of the Ascomycetes, e.g. against Erysiphe graminis on wheat, Erysiphe cichoriacearum on cucumbers, Uncinula necator on vines, Podosphaera leucotricha and Venturia inaequalis on apples and Botrytis cinerea aniner.
• the new connections can also be used in material protection, among other things. to combat molds, such as Trichoderma viride, mold rot, such as Chaetomium globosum, or wood-destroying fungi, such as Coniophora cerebella and Polystictus versicolor.
• molds such as Trichoderma viride, mold rot, such as Chaetomium globosum, or wood-destroying fungi, such as Coniophora cerebella and Polystictus versicolor.
• the fungicidal compositions which can be used contain 0.1 to 95% by weight, preferably 0.5 to 90% by weight, of active compound. Depending on the type of effect desired, the application rates are between 0.01 and 3 kg or more, but preferably between 0.01 and 1 kg of active ingredient / ha.
• the agents are used, for example, in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, scattering agents, granules by spraying, atomizing, dusting, scattering or pouring.
• the application forms depend entirely on the purposes; in any case, they should ensure the finest possible distribution of the active ingredient mixtures.
• L 1 Paraffin tetrahydronaphthalene, alkylated naphthalenes or their derivatives, for example methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, strongly polar solvents, for example dimethylformamide, dimethyl sulfox
• Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) by adding water.
• emulsions, pastes or oil dispersions the substances as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers.
• wetting agents, adhesives, dispersants or emulsifiers, and possibly solvents or oil can also be prepared from active substance and are suitable for dilution with water.
• Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.
• Granules e.g. Coating, impregnation and homogeneous granules can be produced by binding the active ingredients to solid carriers.
• Solid carriers are e.g. Mineral soils such as silica gel, silicas, silicates, talc, kaolin, limestone, lime, chalk, talc, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as e.g. Ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder and other solid carriers.
• Mineral soils such as silica gel, silicas, silicates, talc, kaolin, limestone, lime, chalk, talc, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate
• the active compounds can also be mixed with other known fungicides.
• the fungicidal spectrum of activity is enlarged; a number of these fungicide mixtures have synergistic effects, i.e. the fungicidal activity of the combination product is greater than that of the additive activity of the individual components.
• the comparative agent is the known fungicidal active ingredient 1- (1,2,4-triazol-1-yl) -1- (p-chlorophenacyl) styrene (DE-OS 26 45 617).
• Leaves of potted wheat seedlings of the "Jubilar” variety are sprayed with aqueous emulsions of 80 (% by weight) active ingredient and 20% emulsifier and, after the spray coating has dried on, are dusted with oidia (spores) of the powdery mildew (Erysiphe graminis var. Tritici) .
• the test plants are then placed in a greenhouse at temperatures between 20 and 22 ° C and 75 to 80% relative humidity. After 10 days, the extent of mildew development is determined.
• Leaves of cucumber seedlings washed in pots are sprayed with aqueous emulsions of a mixture of 80% active ingredient and 20% emulsifier and, after the spray coating has dried on, are dusted with oidia (spores) of the cucumber powdery mildew (Erysiphe cichoriacearum).
• the test plants are then placed in a greenhouse at temperatures between 20 and 22 ° C and 75 to 80% relative humidity. After 10 days, the extent of mildew development is determined.
• Pepper seedlings of the "Neusiedler Ideal Elite" variety after up to 5 leaves have developed well, are sprayed to runoff point with 0.05% strength by weight aqueous suspensions containing 80% active ingredient and 20% sodium lignin sulfonate in the dry matter. After the spray coating has dried on, the plants are sprayed with a conidia suspension of the Botrytis cinerea fungus and placed at 22 to 24 ° C. in a chamber with high atmospheric humidity in order to obtain optimum conditions for the development of the fungus. After 5 days, the disease on the untreated control plants developed so much that the resulting leaf necrosis covered most of the leaves.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Agronomy & Crop Science (AREA)
• Pest Control & Pesticides (AREA)
• Plant Pathology (AREA)
• Health & Medical Sciences (AREA)
• Engineering & Computer Science (AREA)
• Dentistry (AREA)
• General Health & Medical Sciences (AREA)
• Wood Science & Technology (AREA)
• Zoology (AREA)
• Environmental Sciences (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Pyrrole Compounds (AREA)

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Publications (3)

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• 1981
  • 1981-01-30 DE DE19813103068 patent/DE3103068A1/de not_active Withdrawn
• 1982
  • 1982-01-18 AT AT82100308T patent/ATE8390T1/de active
  • 1982-01-18 EP EP82100308A patent/EP0057365B1/fr not_active Expired
  • 1982-01-18 DE DE8282100308T patent/DE3260334D1/de not_active Expired
  • 1982-01-26 US US06/342,933 patent/US4521429A/en not_active Expired - Fee Related

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